US4853418A - Polyurethane emulsion, sheet-like porous material making use of the emulsion and production process of the material - Google Patents
Polyurethane emulsion, sheet-like porous material making use of the emulsion and production process of the material Download PDFInfo
- Publication number
- US4853418A US4853418A US07/229,491 US22949188A US4853418A US 4853418 A US4853418 A US 4853418A US 22949188 A US22949188 A US 22949188A US 4853418 A US4853418 A US 4853418A
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- United States
- Prior art keywords
- parts
- polyurethane
- emulsion
- segments
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 94
- 239000004814 polyurethane Substances 0.000 title claims abstract description 94
- 239000000839 emulsion Substances 0.000 title claims abstract description 61
- 239000011148 porous material Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000004945 emulsification Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 43
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 37
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 105
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 239000000543 intermediate Substances 0.000 description 56
- 239000003995 emulsifying agent Substances 0.000 description 30
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 24
- -1 fluorocarbon compound Chemical class 0.000 description 23
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 14
- 229920003009 polyurethane dispersion Polymers 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000011369 resultant mixture Substances 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920006009 resin backbone Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- OBEPNQVBDUZODX-UHFFFAOYSA-N 1,6-diisocyanatohexane;hydrate Chemical compound O.O=C=NCCCCCCN=C=O OBEPNQVBDUZODX-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000921 polyethylene adipate Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- FWWWRCRHNMOYQY-UHFFFAOYSA-N 1,5-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C=C1N=C=O FWWWRCRHNMOYQY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- OJRUSAPKCPIVBY-KQYNXXCUSA-N C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N Chemical compound C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N OJRUSAPKCPIVBY-KQYNXXCUSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229940125961 compound 24 Drugs 0.000 description 1
- 229940125846 compound 25 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical group OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
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- 150000003573 thiols Chemical class 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/283—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum a discontinuous liquid phase emulsified in a continuous macromolecular phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Definitions
- This invention relates to a polyurethane emulsion, a sheet-like porous material and a production process of the porous material. It is a primary object of this invention to provide a sheet-like porous material which is excellent in various properties such as surface smoothness, water repellancy (withstandable water pressure), stain resistance, washability, mechanical properties and vapor permeability and is also good in hand and feel.
- sheet-like porous materials having excellent vapor permeability can be provided by these known processes, these sheet-like porous materials has a porous structure and corollary to this, is accompanied by drawbacks that they are inferior in surface smoothness, hand and feeling and are prone to staining.
- flexibilizer and water repellant such as fluorocarbon compound and fluorine compound
- Such flexibilizer and water repellant are compounds having a relatively low molecular weight and have poor compatibility with polyurethane resins. They hence tend to bleed out to the surface of the porous layer, thereby causing a staining problem that the surface becomes sticky and more susceptible to dust deposition.
- the flexibilizer and water repellant are washed away when the sheet-like porous material is washed repeatedly, leading to a problem in washability that the properties imparted by the flexibilizer and water repellant, such as surface smoothness, hand and feeling, water repellancy (withstandable water pressure) and stain resistance, would be lost.
- the present inventors have carried out an extensive investigation with a view toward meeting the above demand. As a result, it has been found that the use of a specific polyurethane emulsion can solve drawbacks of the conventional techniques, such as those mentioned above, and can thus provide a sheet-like porous material capable of fully meeting the abovementioned demand in the present field of art.
- a polyurethane emulsion which comprises:
- a sheet-like porous material having a porous layer of a polyurethane resin provided on a base material, in which the polyurethane resin has silicone segments and/or fluorocarbon segments as backbones and/or side chains.
- a process for producing a sheet-like porous material by impregnating and/or coating a base material with a water-in-oil type polyurethane emulsion and then gelling and drying the emulsion.
- the polyurethane emulsion comprises:
- silicone compound and/or fluorine compound as flexibilizer(s) and/or water repellant(s) are bound by covalent bonds in the polyurethane.
- the flexibilizer(s) and/or water repellant(s) do not bleed out to the surface along the passage of time and are not washed away by washing, so that excellent surface smoothness and high flexibility, withstandable water pressure, stain resistance and washability can be retained almost permanently.
- the polyurethane resin which is employed in this invention, primarily features this invention and contains silicone segments and/or fluorocarbon segments, is obtained by using a silicone compound having one or more reactive functional groups such as amino, epoxy, hydroxyl, carboxyl and/or thioalcohol groups and/or a fluorine compound having one or more of such functional groups as the entire or partial portion of a polyol, polyisocyanate or chain extender upon obtaining a polyurethane resin by reacting the polyol, polyisocyanate, chain extender, etc.
- a silicone compound having one or more reactive functional groups such as amino, epoxy, hydroxyl, carboxyl and/or thioalcohol groups and/or a fluorine compound having one or more of such functional groups as the entire or partial portion of a polyol, polyisocyanate or chain extender upon obtaining a polyurethane resin by reacting the polyol, polyisocyanate, chain extender, etc.
- polyurethane resin Upon synthesis of the polyurethane resin in the above-described manner, it is possible to synthesize a polyurethane resin containing silicone segments from a silicone compound with one or more reactive functional groups and also another polyurethane resin containing fluorocarbon segments and then to mix and use them at a suitable ratio.
- silicone compound having one or more reactive organic functional groups as described above the following compounds may be mentioned by way of example.
- polyesterpolyols, polyamidepolyamines, polyetherpolyols and the like obtained by reacting them with the below-described polyols, chain extenders, polycarboxylic acids or polyamines may also be used similarly.
- polyols for polyurethanes can all be used as polyols.
- Preferred examples may include those containing a hydroxyl group as a terminal group and having a molecular weight of 300-4,000, such as:
- organic polyisocyanates may all be used.
- the following polyisocyanates may be mentioned as preferred examples.
- urethane prepolymers obtained by reacting these organic polyisocyanates and low molecular polyols or polyamines in such a way that terminal isocyanates are formed.
- chain extenders can all be used, the following chain extenders may be mentioned as preferred examples.
- Polyurethane resins containing silicone segments and/or fluorocarbon segments and blends of polyurethane resins containing silicone segments and polyurethane resins containing fluorocarbon segments, which are obtained from such materials as mentioned above, are all usable in the present invention.
- preferred are those containing silicon segments and/or fluorocarbon segments in a proportion of about 0.2-50 wt.% of the resins. If the total proportion of silicon segments and/or fluorocarbon segments is smaller than about 0.2 wt.%, such a proportion is too small to achieve the objects of the present invention. On the other hand, any proportions greater than about 50 wt.% are not preferred because they result in problems such as reduced adhesion to base materials.
- Their molecular weights may preferably range from 20,000 to 500,000, with 20,000-250,000 being most preferred.
- Such polyurethane resins containing silicone segments and/or fluorocarbon segments can be easily obtained by any one of production processes known to date.
- These polyurethane resins may be prepared without any solvent or may be prepared in an organic solvent. From the process standpoint, it is advantageous to prepare them in an organic solvent useful for the preparation of polyurethane emulsions, in other words, in an organic solvent having a certain degree of miscibility with water, because the resulting reaction mixture may be used as is for the preparation of a polyurethane emulsion.
- Such an organic solent may include methyl ethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate and the like.
- the polyurethane resin When a polyurethane resin is prepared in such an organic solvent, the polyurethane resin is obtained in the form of a solution. It is convenient to adjust the solid content to a range of about 5-60 wt.% by either adding a solvent of the same or different type or removing the solvent.
- the polyurethane resin may be dissolved fully in the organic solvent or may be in the form of a dispersion in which it is contained partially or wholly as crystals. They will hereinafter be called “solutions" for the sake of brevity.
- a suitable amount of a water-in-oil type emulsifier is added to the polyurethane solution as needed. While vigorously stirring the resultant mixture, water is added in a proportion less than the saturation, for example, in an amount of about 50-500 parts by weight per 100 parts by solids weight of solution so that the polyurethane emulsion is obtained.
- any one of water-in-oil type emulsifiers known to date may be used as an emulsifier.
- Particularly preferred are polyurethane-based interface lubricants containing polyoxyethylene chains in a suitable proportion in the molecule.
- the emulsifier may be used preferably in a proportion of about 1-10 parts by weight per 100 parts by solids weight of the polyurethane resin solution.
- the thus-obtained polyurethane emulsion is a cream-like fluid of a milky white color. It retains its stable state even when it is left over for several months as is.
- Such a polyurethane emulsion may be added with one or more of various additives, for example, additives known conventionally such as colorants, crosslinking agents, stabilizers and fillers, as needed.
- any base material may be employed, for example, a desired one of various woven fabrics, knitted fabrics, non-woven fabrics, parting papers, plastic films, metal plates, glass plates and the like.
- any known method may be used such as a coating technique, a dipping technique or a combination thereof.
- the amount of the polyurethane emulsion to be employed for impregnation and/or coating may vary in a wide range, for example, about 2-2,000 g (wet) per m 2 depending what end use will be made.
- the gelling of the polyurethane emulsion applied on the base material and the drying of the thus-gelled polyurethane emulsion and the impregnated and/or coated base material can be achieved in much the same way as the prior art.
- a sheet-like porous polyurethane material having excellent properties can be obtained by drying the impregnated or coated base material at a temperature of about 40°-200° C. or so.
- the sheet-like porous material obtained by using such a polyurethane emulsion according to this invention has a very fine porous structure, has various excellent physical properties along with superb vapor permeability, and is hence useful as a sheet stock for various synthetic leathers and the like, in particular, as apparel, shoes, waterproof fabric, tents, wall paper, flooring, filter materials, filters for air conditioners, and the like.
- the polyurethane resin in the polyurethane emulsion according to this invention contains silicone segments and/or fluorocarbon segments in the backbone and/or side chains of its molecule.
- the silicone segments and/or fluorocarbon segments in the porous layer do not bleed out to the surface of the porous layer along the passage of time, so that the sheet-like porous material can semi-permanently maintain the excellent surface smoothness, hand and feeling, withstandable water pressure, stain resistance and washability.
- Modified Resin Solution (1) a milky white solution [hereinafter called "Modified Resin Solution (1)"] of a modified resin in which the intermediate and polyurethane resin were coupled together.
- Modified Resin Solution (2) a milky white solution [hereinafter called "Modified Resin Solution (2)"] of a modified resin in which the intermediate and polyurethane resin were coupled together.
- Modified Resin Solution (3) a milky white solution [hereinafter called "Modified Resin Solution (3)"] of a modified resin in which the intermediate and polyurethane resin were coupled together.
- Modified Resin Solution (4) a milky white solution [hereinafter called "Modified Resin Solution (4)" of a modified resin in which the intermediate and polyurethane resin were coupled together.
- Modified Resin Solution (5) a milky white solution [hereinafter called "Modified Resin Solution (5)"] of a modified resin in which the intermediate and polyurethane resin were coupled together.
- methyl ethyl ketone Added to 3,600 parts of methyl ethyl ketone were 1,000 parts of 1,4-butaneethylene adipate (average molecular weight: about 1,000; hydroxyl number: 112), 100 parts of a silicone compound of the below-described structure, 31 parts of 1,4-butanediol and 362 parts of diphenylmethane diisocyanate, followed by a reaction at 70° C. for 8 hours to obtain a solution of a polyurethane resin having an average molecular weight of 64,000. The solid content of the solution was 30%.
- methyl ethyl ketone Added to 3,580 parts of methyl ethyl ketone were 1,000 parts of polytetramethylene glycol (average molecular weight: about 1,000; hydroxyl number: 112), 100 parts of a silicone compound of the below-described structure, 24 parts of ethylene glycol and 360 parts of diphenylmethane diisocyanate, followed by a reaction at 70° C. for 9 hours to obtain a solution of a polyurethane resin having an average molecular weight of 53,000. The solid content of the solution was 30%.
- methyl ethyl ketone Added to 6,135 parts of methyl ethyl ketone were 2,000 parts of 1,6-hexamethylene adipate (average molecular weight: about 2,000; hydroxyl number: 56), 200 parts of a silicone compound of the below-described structure, 31 parts of 1,4-butanediol and 346 parts of diphenylmethane diisocyanate, followed by a reaction at 70° C. for 9 hours to obtain a solution of a polyurethane resin having an average molecular weight of 72,000. The solid content of the solution was 30%.
- methyl ethyl ketone Added to 3,435 parts of methyl ethyl ketone were 1,000 parts of 1,4-butaneethylene adipate (average molecular weight: about 1,000; hydroxyl number: 112), 200 parts of a silicone compound of the below-described structure, 31 parts of 1,4-butanediol and 338 parts of diphenylmethane diisocyanate, followed by a reaction at 70° C. for 8 hours to obtain a solution of a polyurethane resin having an average molecular weight of 55,000. The solid content of the solution was 30%.
- Modified polyurethane resin solutions were obtained in a similar manner as in Referential Examples 9-16 except that fluorocarbon compounds and mixtures of fluorocarbon compounds and silicone compounds, which are all given below in Table 1, were used respectively in place of the silicone compounds.
- polyurethane emulsions were prepared by mixing the polyurethane solutions of Referential Examples 9-33 separately along with an emulsifier, organic solvents and water in a homomixer.
- Example 1 Polyurethane Emulsion (1)
- Example 4 Polyurethane Emulsion (4)
- Example 5 Polyurethane Emulsion (5)
- Example 7 Polyurethane Emulsion (7)
- Example 8 Polyurethane Emulsion (8)
- Example 10 Polyurethane Emulsion (10)
- Example 11 Polyurethane Emulsion (11)
- Example 12 Polyurethane Emulsion (12)
- Example 13 Polyurethane Emulsion (13)
- Example 14 Polyurethane Emulsion (14)
- Example 21 Polyurethane Emulsion (21)
- Example 22 Polyurethane Emulsion (22)
- Example 24 Polyurethane Emulsion (24)
- Example 25 Polyurethane Emulsion (25)
- Polyurethane emulsions of Comparative Examples 1-9 were prepared in a similar manner as in Examples 1-9 except that polyurethane resin solutions obtained in the same manner as in Referential Examples 9-17 but containing no silicone segments were used respectively instead of the polyurethane resins containing silicone segments.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Description
H(CF.sub.2 CF.sub.2).sub.5 OH
CF.sub.3 (CF.sub.2 CF.sub.2).sub.3 OH
CF.sub.3 (CF.sub.2 CF.sub.2).sub.3 CH.sub.2 CH.sub.2 SH
TABLE 1 __________________________________________________________________________ Number of Ref. Modification modified Ex. method Fluorocarbon compound Silicone compound resin soln. __________________________________________________________________________ 18 Ref. Ex. 9 5 Parts of the inter- -- 10 mediate of Ref. Ex. 6 19 Ref. Ex. 10 5 Parts of the inter- -- 11 mediate of Ref. Ex. 7 20 Ref. Ex. 11 5 Parts of the inter- -- 12 mediate of Ref. Ex. 8 21 Ref. Ex. 12 5 Parts of the inter- -- 13 mediate of Ref. Ex. 7 22 Ref. Ex. 13 5 Parts of the inter- -- 14 mediate of Ref. Ex. 8 23 Ref. Ex. 14 50 Parts of a compound -- 15 of the below-described structure A 24 Ref. Ex. 15 100 Parts of a com- -- 16 pound of the below- described structure B 25 Ref. Ex. 16 100 Parts of a com- -- 17 pound of the below- described structure C 26 Ref. Ex. 9 5 Parts of the inter- 5 Parts of the inter- 18 mediate of Ref. Ex. 1 mediate of Ref. Ex. 6 27 Ref. Ex. 10 5 Parts of the inter- 5 Parts of the inter- 19 mediate of Ref. Ex. 2 mediate of Ref. Ex. 7 28 Ref. Ex. 11 5 Parts of the inter- 5 Parts of the inter- 20 mediate of Ref. Ex. 3 mediate of Ref. Ex. 8 29 Ref. Ex. 12 5 Parts of the inter- 5 Parts of the inter- 21 mediate of Ref. Ex. 4 mediate of Ref. Ex. 7 30 Ref. Ex. 13 5 Parts of the inter- 5 Parts of the inter- 22 mediate of Ref. Ex. 5 mediate of Ref. Ex. 8 31 Ref. Ex. 14 100 Parts of a com- 50 Parts of a compound 23 pound of the below- of the below-described described structure D structure B 32 Ref. Ex. 15 100 Parts of a com- 50 Parts of a compound 24 pound of the below- of the below-described described structure E structure B 33 Ref. Ex. 16 200 Parts of a com- 50 Parts of a compound 25 pound of the below- of the below-described described structure F structure C __________________________________________________________________________ ##STR24##
______________________________________ Polyurethane solution (1) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts ______________________________________
______________________________________ Polyurethane solution (2) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (3) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 150 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (4) 100 parts PO/EO Block copolymer type emulsifier 4 parts Dioxane 10 parts Toluene 10 parts Xylene 20 parts Water 70 parts ______________________________________
______________________________________ Polyurethane solution (5) 100 parts Urethane type emulsifier 1 part Methyl isobutyl ketone 20 parts Toluene 20 parts Water 75 parts ______________________________________
______________________________________ Polyurethane solution (6) 100 parts PO/EO Block copolymer type emulsifier 1 part tetrahydrofuran 20 parts Toluene 20 parts Water 60 parts ______________________________________
______________________________________ Polyurethane solution (7) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts ______________________________________
______________________________________ Polyurethane solution (8) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (9) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 150 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (10) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts ______________________________________
______________________________________ Polyurethane solution (11) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (12) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 150 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (13) 100 parts PO/EO Block copolymer type emulsifier 4 parts Dioxane 10 parts Toluene 10 parts Xylene 20 parts Water 70 parts ______________________________________
______________________________________ Polyurethane solution (14) 100 parts Urethane type emulsifier 1 part Methyl isobutyl ketone 20 parts Toluene 20 parts Water 75 parts ______________________________________
______________________________________ Polyurethane solution (15) 100 parts PO/EO Block copolymer type emulsifier 1 part Tetrahydrofuran 20 parts Toluene 20 parts Water 60 parts ______________________________________
______________________________________ Polyurethane solution (16) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts ______________________________________
______________________________________ Polyurethane solution (17) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (18) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts ______________________________________
______________________________________ Polyurethane solution (19) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (20) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 150 parts Toluene 20 parts Water 80 parts ______________________________________
______________________________________ Polyurethane solution (21) 100 parts PO/EO Block copolymer type emulsifier 4 parts Dioxane 10 parts Toluene 10 parts Xylene 20 parts Water 70 parts ______________________________________
______________________________________ Polyurethane solution (22) 100 parts Urethane type emulsifier 1 part Methyl isobutyl ketone 20 parts Toluene 20 parts Water 75 parts ______________________________________
______________________________________ Polyurethane solution (23) 100 parts PO/EO Block copolymer type emulsifier 1 part Tetrahydrofuran 20 parts Toluene 20 parts Water 60 parts ______________________________________
______________________________________ Polyurethane solution (24) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts ______________________________________
______________________________________ Polyurethane solution (25) 100 parts Urethane type emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts ______________________________________
TABLE 2 ______________________________________ Viscosity Solid content Emulsion No. (25° C., cps) (%) ______________________________________ Example 1 22,000 14.1 2 17,000 14.4 3 130 9.2 4 21,000 15.1 5 20,000 14.4 6 15,000 15.4 7 20,000 14.1 8 15,000 14.4 9 180 9.2 10 20,000 14.2 11 18,500 14.5 12 150 9.3 13 21,500 15.0 14 21,000 14.3 15 16,100 15.5 16 20,500 14.0 17 14,500 14.4 18 21,000 14.2 19 17,500 14.4 20 140 9.2 21 22,000 14.9 22 20,000 14.4 23 14,600 15.5 24 21,000 14.2 25 15,200 14.5 Comp. Ex. 1 21,000 14.2 2 16,000 14.4 3 140 9.2 4 20,000 14.9 5 19,000 14.4 6 16,000 15.5 7 19,000 14.2 8 17,000 14.5 9 160 9.2 ______________________________________
TABLE 3 __________________________________________________________________________ Emulsion Ex. No. Base material Coated/impregnated amount Drying conditions __________________________________________________________________________ 26 1 Parting paper Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 27 2 Parting paper Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 28 3 Nonwoven fabric Impregnated at 1000 g/m.sup.2 90° C. × 3 min + 140° C. × 3 min 29 4 Cotton fabric Coated at 400 g/m.sup.2 140° C. × 3 min 30 5 Nylon taffeta Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 31 6 Tufted T/R fabric Coated at 600 g/m.sup.2 120° C. × 4 min 32 7 Polyester taffeta Coated at 200 g/m.sup.2 140° C. × 2 min 33 8 Tufted T/R fabric Coated at 600 g/m.sup.2 120° C. × 4 min 34 9 Nonwoven fabric Impregnated at 1000 g/m.sup.2 120° C. × 5 min 35 10 Parting paper Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 36 11 Parting paper Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 37 12 Nonwoven fabric Impregnated at 1000 g/m.sup.2 90° C. × 3 min + 140° C. × 3 min 38 13 Cotton fabric Coated at 400 g/m.sup.2 140° C. × 3 min 39 14 Nylon taffeta Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 40 15 Tufted T/R fabric Coated at 600 g/m.sup.2 120° C. × 4 min 41 16 Polyester taffeta Coated at 200 g/m.sup.2 140° C. × 2 min 42 17 Tufted T/R fabric Coated at 600 g/m.sup.2 120° C. × 4 min 43 18 Parting paper Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 44 19 Parting paper Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 45 20 Nonwoven fabric Impregnated at 1000 g/m.sup.2 90° C. × 3 min + 140° C. × 3 min 46 21 Cotton fabric Coated at 400 g/m.sup.2 140° C. × 3 min 47 22 Nylon taffeta Coated at 200 g/m.sup.2 80° C. × 2 min + 125° C. × 2 min 48 23 Tufted T/R fabric Coated at 600 g/m.sup.2 120° C. × 3 min 49 24 Polyester taffeta Coated at 200 g/m.sup.2 140° C. × 4 min 50 25 Tufted T/R fabric Coated at 600 g/m.sup.2 120° C. × 4 __________________________________________________________________________ min
TABLE 4 ______________________________________ V Property I II III IV Before After ______________________________________ 26 550 ○ 9550 -- 100 70 27 410 ○ 9370 -- 100 70 28 450 ○ 6930 6000 100 50 29 380 ○ 8560 6500 100 70 30 450 ○ 6520 4500 100 50 31 350 ○ 7230 6000 100 70 32 400 ○ 7520 5000 100 50 33 370 ○ 8100 6200 100 50 34 570 ○ 8210 6000 100 70 35 570 ○ 8250 -- 100 70 36 450 ○ 8570 -- 100 70 37 500 ○ 6140 6000 100 50 38 400 ○ 8210 6500 100 70 39 510 ○ 6100 4500 100 50 40 620 ○ 7000 6000 100 70 41 600 ○ 7120 5000 100 50 42 650 ○ 7600 6200 100 50 43 580 ○ 9150 -- 100 70 44 510 ○ 9070 -- 100 70 45 530 ○ 6230 6000 100 70 46 450 ○ 8360 6500 100 70 47 520 ○ 6510 4500 100 70 Example 48 650 ○ 7180 6000 100 70 49 630 ○ 7080 5000 100 50 50 660 ○ 7590 6500 100 70 Comparative Example 10 30 ○ 6270 -- 0 0 11 25 ○ 5820 -- 0 0 12 35 Δ 4050 4500 0 0 13 40 X 5800 5000 0 0 14 30 X 2960 3500 0 0 15 28 Δ 6100 5000 0 0 16 37 X 6890 3500 0 0 17 31 X 5120 5000 0 0 18 28 Δ 6620 5000 0 0 ______________________________________ Note: I Surface smoothness (surface durability): Each resin layer was rubbed with gauze under a load of 500 g. Its surface smoothness is expressed in terms of strokes counted until the resin layer was broken. II Hand and feeling: ○ : soft, Δ: slightly hard, X: hard. III Moisture permeability (g/m.sup.2 · 24 hrs, measured by the procedure prescribed in JIS Z0208B). IV Withstandable water pressure (mm H.sub.2 O). V Washability (water repellancy both before and after washing).
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62198320A JPH0637754B2 (en) | 1987-08-10 | 1987-08-10 | Porous sheet material and method for producing the same |
JP62-198320 | 1987-08-10 |
Publications (1)
Publication Number | Publication Date |
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US4853418A true US4853418A (en) | 1989-08-01 |
Family
ID=16389155
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US07/229,491 Expired - Fee Related US4853418A (en) | 1987-08-10 | 1988-08-08 | Polyurethane emulsion, sheet-like porous material making use of the emulsion and production process of the material |
Country Status (4)
Country | Link |
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US (1) | US4853418A (en) |
EP (1) | EP0303876B1 (en) |
JP (1) | JPH0637754B2 (en) |
DE (1) | DE3880583T2 (en) |
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US5302459A (en) * | 1991-08-01 | 1994-04-12 | Cheil Synthetics Inc. | Method for preparation of polyester films with good release and slip properties |
US5554673A (en) * | 1993-11-29 | 1996-09-10 | Polygenex International, Inc. | Dip molded polyurethane film compositions |
US5621042A (en) * | 1990-12-17 | 1997-04-15 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Coating compositions |
US5700868A (en) * | 1995-07-25 | 1997-12-23 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Back-side coating formulations for heat-sensitive recording materials and heat-sensitive recording materials having a back layer coated therewith |
WO2002014443A2 (en) * | 2000-08-14 | 2002-02-21 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
US6384174B2 (en) | 2000-03-07 | 2002-05-07 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Fluorine-containing diols and use thereof |
US6383564B1 (en) * | 1998-12-24 | 2002-05-07 | Nitto Kogyo Co., Ltd. | Method for forming a porous covering layer on a substrate |
US6555230B2 (en) | 2000-03-31 | 2003-04-29 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Artificial leather |
US20030136938A1 (en) * | 2001-12-04 | 2003-07-24 | 3M Innovative Properties Company | Repellent fluorochemical compositions |
US20070111620A1 (en) * | 2003-12-15 | 2007-05-17 | Teijin Cordley Limited | Leather-like sheet material and process for the production thereof |
US20100119775A1 (en) * | 2007-03-21 | 2010-05-13 | Basf Se | Aqueous dispersions and their use for the production of sheet-like substrates |
Families Citing this family (6)
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US4942212A (en) * | 1988-01-20 | 1990-07-17 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Polyurethane resin and heat-sensitive recording medium |
GB9009409D0 (en) * | 1990-04-26 | 1990-06-20 | Dow Corning | Film-forming copolymers and their use in water vapour permeable coatings |
IT1245467B (en) * | 1991-03-19 | 1994-09-20 | Lorica Spa | PROCEDURE FOR OBTAINING A SHEET PRODUCT WITH AN APPEARANCE SIMILAR TO THAT OF NATURAL LEATHER, STARTING FROM A SYNTHETIC LEATHER MADE OF COMPOSITE MATERIAL |
NZ332019A (en) * | 1996-03-27 | 2000-02-28 | Novartis Ag | High water content porous polymer comprising a perfluoropolyether unit |
US6322851B1 (en) * | 1998-06-30 | 2001-11-27 | Kuraray Co., Ltd. | Manufacturing process for leather-like sheet |
US6890360B2 (en) * | 2001-12-17 | 2005-05-10 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
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US5621042A (en) * | 1990-12-17 | 1997-04-15 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Coating compositions |
US5302459A (en) * | 1991-08-01 | 1994-04-12 | Cheil Synthetics Inc. | Method for preparation of polyester films with good release and slip properties |
US5554673A (en) * | 1993-11-29 | 1996-09-10 | Polygenex International, Inc. | Dip molded polyurethane film compositions |
US5571567A (en) * | 1993-11-29 | 1996-11-05 | Polygenex International, Inc | Dip molded polyurethane film methods |
US5700868A (en) * | 1995-07-25 | 1997-12-23 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Back-side coating formulations for heat-sensitive recording materials and heat-sensitive recording materials having a back layer coated therewith |
US5908808A (en) * | 1995-07-25 | 1999-06-01 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Back-side coating formulations for heat-sensitive recording materials and heat-sensitive recording materials having a back layer coated therewith |
US6383564B1 (en) * | 1998-12-24 | 2002-05-07 | Nitto Kogyo Co., Ltd. | Method for forming a porous covering layer on a substrate |
US6384174B2 (en) | 2000-03-07 | 2002-05-07 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Fluorine-containing diols and use thereof |
US6555230B2 (en) | 2000-03-31 | 2003-04-29 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Artificial leather |
WO2002014443A2 (en) * | 2000-08-14 | 2002-02-21 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
WO2002014443A3 (en) * | 2000-08-14 | 2002-08-29 | 3M Innovative Properties Co | Urethane-based stain-release coatings |
US20030136938A1 (en) * | 2001-12-04 | 2003-07-24 | 3M Innovative Properties Company | Repellent fluorochemical compositions |
US7056846B2 (en) | 2001-12-04 | 2006-06-06 | 3M Innovative Properties Company | Repellent fluorochemical compositions |
US20070111620A1 (en) * | 2003-12-15 | 2007-05-17 | Teijin Cordley Limited | Leather-like sheet material and process for the production thereof |
US20100119775A1 (en) * | 2007-03-21 | 2010-05-13 | Basf Se | Aqueous dispersions and their use for the production of sheet-like substrates |
US9234071B2 (en) * | 2007-03-21 | 2016-01-12 | Basf Se | Aqueous dispersions and their use for the production of sheet-like substrates |
Also Published As
Publication number | Publication date |
---|---|
EP0303876B1 (en) | 1993-04-28 |
JPH0637754B2 (en) | 1994-05-18 |
DE3880583D1 (en) | 1993-06-03 |
JPS6445877A (en) | 1989-02-20 |
DE3880583T2 (en) | 1993-11-25 |
EP0303876A1 (en) | 1989-02-22 |
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